Miscible solvent system and method for making same

ABSTRACT

A miscible solvent system and method for making same having a composition between about 10 to about 90 weight percent PCBTF and between about 10 to about 90 weight percent fluorinated solvent. The miscible solvent system may be combined with boron nitride powder to create a bulk paint system. Further the miscible solvent system may be combined with a propellant to create an aerosol system. The miscible solvent system, bulk paint system, and aerosol system may be nonflammable or flammable and contain VOCs or be VOC free.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application to co-pending U.S. patentapplication Ser. No. 14/069,964 filed Nov. 1, 2013, which isincorporated herein by reference.

BACKGROUND

The present invention relates generally to the field of solvents. Moreparticularly, the present invention relates to a solvent system having aparachlorobenzotrifluoride (PCBTF) component and a fluorinated solventcomponent that is preferably nonflammable and miscible in allproportions. Furthermore, the solvent system of the present inventionpreferably has low levels of volatile organic compounds (VOCs) and issafe and relatively environmentally friendly.

Solvents are traditionally used for cleaning, degreasing, coating, andbonding or debonding and are frequently used in connection withultrasonic cleaning and vapor cleaning. Solvent systems have beensignificantly restricted over the past couple of decades dues toenvironmental and safety concerns. For example, it is highly preferredthat solvents have a high flash point and are thereby minimallyflammable or nonflammable, have low toxicity, have little global warmingpotential, and produce low or no hazardous air pollutants and VOCs.Further, when solvents are used for cleaning or degreasing valuableproducts such as electronic and aerospace components, it is highlypreferred that such solvents are fast drying and exhibit high dissolvingcapabilities so that the solvents do not harm the components.

While various solvents are known, there is a need for a nonflammable andhighly miscible solvent system that exhibits environmentally friendlycharacteristics such as low levels of VOCs.

SUMMARY

The present invention includes a miscible solvent system. In oneembodiment of the invention, the miscible solvent system has acomposition of between about 10 to about 90 weight percent PCBTF andbetween about 10 to about 90 weight percent fluorinated solvent. Inanother embodiment of the invention, the solvent system has acomposition of between about 20 to about 40 weight percent PCBTF andbetween about 60 to about 80 weight percent fluorinated solvent. In yetanother embodiment of the invention, the solvent system has acomposition of between about 67 through 69 weight percent fluorinatedsolvent and between about 31 through 33 weight percent PCBTF. Further,another embodiment of the present invention includes a miscible solventsystem having a composition between about 50 through 59 weight percentfluorinated solvent and between about 41 through 50 weight percentPCBTF. Yet another embodiment of the present invention includes amiscible solvent system having a composition between about 40 to about44 weight percent fluorinated solvent, between about 36 to about 40weight percent PCBTF, and between about 18 to about 22 weight percentacetone.

The miscible solvent system may include various fluorinated solventsincluding those that contain trans-1,2-DCE and those that aretrans-1,2-DCE free. Further, the miscible solvent system may beflammable or nonflammable and contain VOCs or be VOC free. The misciblesolvent system may be combined with suspenders, binders, fillers such asboron nitride powder, paints, propellants, and/or viscosity modifiers.Further, the miscible solvent system of the present invention may beused as a cleaner, a paint carrier, a coating, a debonder, or a bondingagent and may be inserted into an aerosol container for spraying or usedas a bulk paint.

The present invention also includes a bulk paint system. In oneembodiment of the invention, the bulk paint system includes boronnitride powder and a miscible solvent having a composition of betweenabout 10 to about 90 weight percent PCBTF and between about 10 to about90 weight percent fluorinated solvent. In another embodiment of theinvention, the bulk paint system includes boron nitride powder and amiscible solvent having a composition of between about 20 to about 40weight percent PCBTF and between about 60 to about 80 weight percentfluorinated solvent. In yet another embodiment of the invention, thebulk paint system includes boron nitride powder and a miscible solventhaving a composition of between about 67 through 69 weight percentfluorinated solvent and between about 31 through 33 weight percentPCBTF. Further, another embodiment of the present invention includes abulk paint system including boron nitride powder and a miscible solventhaving a composition between about 50 through 59 weight percentfluorinated solvent and between about 41 through 50 weight percentPCBTF. In yet another embodiment of the present invention, the bulkpaint system includes a miscible solvent having a composition betweenabout 40 through 60 weight percent PCBTF and between about 40 through 60weight percent fluorinated solvent. The bulk paint system of the presentinvention may include between about 1 to about 25 weight percent boronnitride powder and between about 75 to about 99 weight percent misciblesolvent. In one embodiment of the present invention, the bulk paintsystem includes 20 weight percent boron nitride powder and in anotherembodiment, the bulk paint system includes 16 weight percent boronnitride powder.

The bulk paint system may include various fluorinated solvents includingthose that contain trans-1,2-DCE and those that are trans-1,2-DCE free.Further, the bulk paint system may be flammable or nonflammable andcontain VOCs or be VOC free. The bulk paint system may be combined withsuspenders, binders, additional fillers, paints, propellants, and/orviscosity modifiers. Further, the bulk paint system of the presentinvention may be combined with a propellant and inserted into an aerosolcontainer for spraying as an aerosol based spray paint.

The present invention also includes an aerosol system that may beinserted into an aerosol spray container. In one embodiment of theinvention, the aerosol system includes a propellant and a misciblesolvent having a composition of between about 10 to about 90 weightpercent PCBTF and between about 10 to about 90 weight percentfluorinated solvent. In another embodiment of the invention, the aerosolsystem includes a propellant and a miscible solvent having a compositionof between about 20 to about 40 weight percent PCBTF and between about60 to about 80 weight percent fluorinated solvent. In yet anotherembodiment of the invention, the aerosol system includes a propellantand a miscible solvent having a composition of between about 67 through69 weight percent fluorinated solvent and between about 31 through 33weight percent PCBTF. Further, another embodiment of the presentinvention includes an aerosol system including a propellant and amiscible solvent having a composition between about 50 through 59 weightpercent fluorinated solvent and between about 41 through 50 weightpercent PCBTF. The aerosol system of the present invention may includebetween about 20 to about 50 weight percent propellant and between about45 to about 80 weight percent miscible solvent. Further, the aerosolsystem of the present invention may include between about 32 to about 45weight percent propellant and between about 46 to about 69 weightpercent miscible solvent.

The aerosol system may include various fluorinated solvents includingthose that contain trans-1,2-DCE and those that are trans-1,2-DCE free.Further, the aerosol system may be flammable or nonflammable and containVOCs or be VOC free. The aerosol system may be combined with suspenders,binders, fillers such as boron nitride powder, paints, additionalpropellants, and/or viscosity modifiers. Further, the aerosol system ofthe present invention may be used as a cleaner, a coating, or a paint.In one embodiment of the present invention, the aerosol system includesbetween about 32 to about 45 weight percent propellant, between about 46to about 62 weight percent miscible solvent system, and between about 7to about 9 weight percent boron nitride powder.

The present invention also includes a method of manufacturing a misciblesolvent system. In one embodiment of the invention, the method includesthe steps of providing a composition having between about 10 to about 90weight percent PCBTF and between about 10 to about 90 weight percentfluorinated solvent and then mixing the composition to create a miscibleliquid. A boron nitride powder may also be provided and mixed with themiscible liquid to create a bulk paint. Further, a propellant may beadded and mixed with the miscible liquid to create an aerosol. Theaerosol may be inserted into an aerosol container capable of sprayingthe aerosol and/or mixed with boron nitride powder to create an aerosolmixture.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent includes1,1,1,2,2,3,4,5,5,5-decafluoropentane and trans-1,2-DCE.

FIG. 2 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent is a blend of hydrofluoroethers(HFEs) including ethyl nonafluorobutyl ether (C₆H₅F₉O), ethylnonafluoroisobutyl ether (C₆H₅F₉O), methyl nonafluorobutyl ether(C₅H₃F₉O), methyl nonafluoroisobutyl ether (C₅H₃F₉O), and trans-1,2-DCE.

FIG. 3 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent is methoxy-nonafluorobutane.

FIG. 4 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent is1,1,1,2,2,3,4,5,5,5-decafluoropentane.

DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS

The present invention relates to a solvent system and composition. Thesolvent system is preferably highly miscible and may be flammable,nonflammable, or have low flammability. Further, the solvent system ispreferably VOC free or has low VOC levels thereby making it relativelysafe and environmentally friendly. The solvent system of the presentinvention preferably exhibits exceptional cleaning capabilities whilealso being capable of acting as a carrier or vehicle for paints and/orcoatings. Although primarily described herein in terms of its use as acleaner, paint vehicle, debonder, or bonding agent, it will be clearthat the solvent system and composition of the present invention mayhave various other uses. Further, the solvent system of the presentinvention may also be combined with suspenders, binders, and/or fillersso that it can be used in an aerosol can and yield a preferablynonflammable aerosol cleaner or coating.

Unless otherwise stated, the following terms used in the specificationand claims have the meanings given below.

As used herein unless otherwise stated, the term “flash point” refers tothe lowest temperature at which a material can vaporize to form anignitable mixture in air.

As used herein unless otherwise stated, the term “flammable” refers toliquids with a flash point less than about 100 degree Fahrenheit (38degrees Celsius) when an ignition source is used.

As used herein unless otherwise stated, the term “combustible” refers toliquids with a flash point less than about 200 degrees Fahrenheit (93degrees Celsius) but greater than about 100 degree Fahrenheit (38degrees Celsius).

As used herein unless otherwise stated, the term “nonflammable” refersto liquids with a flash point greater than about 200 degree Fahrenheit(93 degrees Celsius).

As used herein unless otherwise stated, the term “miscible” refers towhen two or more chemicals are mixed together at prescribed percentagesthey do not separate into two or more phases.

As used herein unless otherwise stated, the term “miscible solvent”refers to a solvent in which all of the constituents are misciblewithout the inclusion of a surfactant or emulsifier to preventseparation of the mixture into two or more phases.

As used herein unless otherwise stated, the terms “VOC free,” “VOCexempt,” and “Non-VOC” are used interchangeably and refer to the UnitedStates classifications concerning the levels of volatile organiccompounds in liquids and solvents.

The solvent system and composition of the present invention is generallycomposed of at least two primary components: aparachlorobenzotrifluoride (PCBTF) and a fluorinated solvent. In oneembodiment of the present invention, PCBTF is between approximately 10to approximately 90 weight percent of the solvent composition.Furthermore, the solvent composition includes approximately 10 toapproximately 90 weight percent fluorinated solvent.

PCBTF is an organic chemical compound with the molecular formulaC₇H₄ClF₃. Oxcol 100™ is a brand name of a commonly sold PCBTF. PCBTF isa VOC-exempt liquid that has environmentally friendly properties and isclassified as having combustible properties. The flash point of PCBTF istypically about 109 degrees Fahrenheit (approximately 43 degreesCelsius).

Various fluorinated solvents, such as hydrofluorocarbons (HFCs) and/orhydrofluoroethers (HFEs), may be used to compose the solvent system ofthe present invention. As a more particular example,methoxy-nonafluorobutane, also known as HFE 7100, may be used. HFE 7100has a molecular formula of C₄F₉OCH₃ or C₅F₉O H₃ and is frequently soldunder the brand name Novec 7100™ Another fluorinated solvent that may beused in connection with the present invention includes1,1,1,2,2,3,4,5,5,5-decafluoropentane, which may be sold under the brandname Vertrel XF™ and has a molecular formula of C₅F₁₀H₂.

The fluorinated solvent of the present invention may also include acombination of solvents or may be combined with other chemicalcompositions. For example, a fluorinated solvent may be combined with1,2-dichloroethylene, also commonly known as 1,2-dichloroethene and1,2-DCE, and having a molecular formula C2H2Cl2 or CClHCClH. Eithergeometric isomer of 1,2-DCE, including cis-1,2-DCE or trans-1,2-DCE, maybe used. By itself, 1,2-DCE is very flammable with a flash point ofapproximately 55.4 degrees Fahrenheit (13 degrees Celsius). Further,1,2-DCE, while not considered a carcinogen, is considered a VOC andtherefore is not a preferred component at least in large quantities.

Vertrel-MCA™ is a brand name of a fluorinated solvent incorporating1,1,1,2,2,3,4,5,5,5-decafluoropentane in combination with trans-1,2-DCEthat may be used in the present invention. The Vertrel-MCA™ compositionincludes approximately 61 through 63 weight percent1,1,1,2,2,3,4,5,5,5-decafluoropentane and approximately 37 through 39weight percent trans-1,2-DCE. Alternatively a combination or blend ofhydrofluoroethers (HFEs), such as ethyl nonafluorobutyl ether (C₆H₅F₉O),ethyl nonafluoroisobutyl ether (C₆H₅F₉O), methyl nonafluorobutyl ether(C₅H₃F₉O), and methyl nonafluoroisobutyl ether (C₅H₃F₉O), may be used tocompose the fluorinated solvent. Novec 72DE™ is a brand name of asuitable blend of the above disclosed HFEs, which also includestrans-1,2-DCE. Novec 72DE™ includes approximately 68 through 72 weightpercent trans-1,2-DCE, approximately 4 through 16 weight percent ethylnonafluorobutyl ether, approximately 4 through 16 weight percent ethylnonafluoroisobutyl ether, approximately 2 through 8 percent methylnonafluorobutyl ether, and approximately 2 through 8 percent methylnonafluoroisobutyl ether. A blend of hydrofluorocarbons may also be usedsuch as a combination of 1,1,1,3,3-pentafluorobutane (C₄H₅F₅), alsoknown as HFC-365mfc, and 1,1,1,2,3,3,3-heptafluoropropane (C₃HF₇), alsoknown as HFC-227ea. Solkane 365/227™ is a brand name of a suitable blendof the above disclosed HFCs, which may be used with or without theaddition of trans-1,2-DCE. In one embodiment, the blend ofhydrofluorocarbons includes approximately 7 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 93 weight percent1,1,1,3,3-pentafluorobutane. In another embodiment, the blend ofhydrofluorocarbons includes approximately 13 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 87 weight percent1,1,1,3,3-pentafluorobutane. Additional fluorinated solventcompositions, including fluorinated solvent combinations, may be used aswill be understood by those of skill in the arts without departing fromthe scope of the present invention.

The solvent system of the present invention may be used for manyapplications and determination of a composition typically depends on theparticular use of the solvent system. For example, one composition mayhave properties better suited for cleaning while a different compositionmay have properties better suited for mixing with concentrated paints orcoatings to act as a carrier for such concentrated paints or coatings.Further, one composition may have properties better suited forultrasonic cleaning while a different composition may have propertiesbetter suited for cleaning electronics. Moreover, certain compositionsmay be used as a bonding agent while additional compositions may be usedas a debonder.

As discussed above, the solvent system and composition of the presentinvention includes approximately 10 to approximately 90 weight percentPCBTF and approximately 10 to approximately 90 weight percentfluorinated solvent. It is preferred to include no more than 90 weightpercent HFC and/or HFE solvents because of the traditionally high costsassociated with purchasing these products. It is also preferred toinclude no more than 90 weight percent PCBTF because PCBTF amounts abovethis may significantly increase the evaporating time of the solvent,which is typically not preferred. It is also preferred that the PCBTFand fluorinated solvent is miscible in all proportions when mixed. Incertain embodiments, the solvent system is nonflammable while inalternative embodiments the solvent system is flammable. Furthermore, incertain embodiments of the present invention, the solvent system is VOCfree while in alternative embodiments, the solvent system contains VOCs;however, it is preferred that VOC containing components are incorporatedat minimum levels to reduce the overall levels of VOC in the solventsystem.

For certain applications and fluorinated solvents, the solvent systemand composition of the present invention preferably includesapproximately 20 to approximately 40 weight percent PCBTF andapproximately 60 to approximately 80 weight percent fluorinated solvent.Further for such applications and fluorinated solvents, the solventsystem and composition may even more preferably include approximately 31to approximately 33 weight percent PCBTF and approximately 67 toapproximately 69 weight percent fluorinated solvent. For an alternativeapplication, the solvent system and composition of the present inventionpreferably includes approximately 40 to approximately 50 weight percentPCBTF and approximately 50 to approximately 60 weight percentfluorinated solvent. Further for such applications, the solvent systemand composition may even more preferably include approximately 41 toapproximately 50 weight percent PCBTF and approximately 50 toapproximately 59 weight percent fluorinated solvent.

The solvent system and composition of the present invention may betrans-1,2-DCE free to reduce or eliminate the presence of VOCs.Alternatively, the solvent system may include trans-1,2-DCE to utilizeazeotropes and thereby increase the dissolving ability and compatibilityof the solvent system with typical binders, suspenders, and viscositymodifiers. Incorporating trans-1,2-DCE may also assist with creating asingle phase mixture that is less likely to result in a flammableoccurrence due to varying dissolving chemistries. A lower VOC level maybe achieved if smaller quantities of trans-1,2-DCE are incorporated,such as less than 38 weight percent trans-1,2-DCE of the totalfluorinated solvent system. Trans-1,2-DCE levels may however range at orabove 72 weight percent of the total fluorinated solvent system withoutdeparting from the spirit and scope of the present invention.

Examples of fluorinated solvents that can be used independent oftrans-1,2-DCE include HFE 7100, 1,1,1,2,2,3,4,5,5,5-decafluoropentane,and HFC blends such as a combination of 1,1,1,3,3-pentafluorobutane and1,1,1,2,3,3,3-heptafluoropropane. In one embodiment, the blend ofhydrofluorocarbons includes approximately 7 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 93 weight percent1,1,1,3,3-pentafluorobutane. In another embodiment, the blend ofhydrofluorocarbons includes approximately 13 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 87 weight percent1,1,1,3,3-pentafluorobutane. Examples of fluorinated solvents that mayincorporate trans-1,2-DCE include 1,1,1,2,2,3,4,5,5,5-decafluoropentane,blends of hydrofluoroethers such as ethyl nonafluorobutyl ether, ethylnonafluoroisobutyl ether, methyl nonafluorobutyl ether, and methylnonafluoroisobutyl ether, and as discussed above HFE 7100. In oneembodiment, the fluorinated solvent includes between about 61 to about63 weight percent 1,1,1,2,2,3,4,5,5,5-decafluoropentane and betweenabout 37 to about 39 weight percent trans-1,2-DCE. In anotherembodiment, the fluorinated solvent includes about 68 to about 72 weightpercent trans-1,2-DCE and about 28 to about 32 weight percent mixture ofhydroflouroethers. Further, in one embodiment, the blend ofhydroflouroethers includes approximately 4 through 16 weight percent ofethyl nonafluorobutyl ether, approximately 4 through 16 weight percentof ethyl nonafluoroisobutyl ether, approximately 2 through 8 weightpercent of methyl nonafluorobutyl ether, and approximately 2 through 8weight percent of methyl nonafluoroisobutyl ether. In yet anotherembodiment, the fluorinated solvent includes about 90 weight percenttrans-1,2-DCE and 10 weight percent HFE 7100 (sold under the brand nameNovec 71D90).

Additional fluorinated solvents may be used in connection with thesolvent system of the present invention either with or without theincorporation of trans-1,2-DCE without departing from the spirit andscope of the present invention. Furthermore, trans-1,2-DCE may beincorporated independent of the fluorinated solvent.

Additives and agents, such as organic containing binders, suspenders,and viscosity modifiers may be incorporated into the solvent system ofthe present invention. Such additives may be those that are typicallyused in paints and coatings. Examples of typical binders and/orsuspenders include cellulosics, including hydroxypropylcellulose orethyl cellulose, and polyvinylpyrrolidone. The viscosity modifiers arepreferably those that are compatible with non-aqueous fluids andliquids, such as organoclays. Compatible powder additives such as boronnitride powders and metal powders may also be incorporated into thesolvent system of the present invention. Furthermore additives such asalternatives to trans-1,2-DCE may be incorporated into the solventsystem. Example trans-1,2-DCE alternatives include acetone, octylalcohol (CAS 111-87-5), tea tree oil (CAS 68647-73-4), polyalkyleneglycol derivative (CAS 9038-95-3), alpha terpineol (CAS 98-55-5), andcombinations thereof. When additives such as acetone are incorporated,the solvent system may become flammable.

When such additives or agents are incorporated, the total weightpercents of PCBTF and fluorinated solvent for the entire composition maybe proportionally reduced. In one embodiment, the solvent system andcomposition may include approximately 35 to approximately 50 weightpercent fluorinated solvent, approximately 30 to approximately 45 weightpercent PCBTF, and approximately 15 to approximately 30 weight percentadditives. In yet another embodiment, when an additive such as acetoneis incorporated, the solvent system and composition preferably includesapproximately 40 to approximately 44 weight percent fluorinated solvent,approximately 36 to approximately 40 weight percent PCBTF, andapproximately 18 to approximately 22 weight percent acetone.

Selection of a particular composition for a solvent system will furthertypically depend on the preferred evaporation and drying rate as well asthe cost of the solvent system. With respect to the cost of the solventsystem, 1,2-DCE and PCBTF are typically significantly less expensivethan the relatively pure HFE and HFC solvents. Thus, it is oftenpreferred to include higher levels of 1,2-DCE and PCBTF in the solventsystem. Depending on the use of the solvent system, differentevaporation and drying rates are preferred. For instance, slower dryingmay be preferred for solvent cleaning because it allows organic residueslonger to be dissolved and then flow off.

The solvent system and composition of the present invention may comprisea filler material such as boron nitride powder solids and/or othercompatible powder additives such as metal powders. Further, the solventsystem may include a propellant, such as HFO-1234ze or HFC-134a, forinsertion of the solvent system into an aerosol can for spraying thesolvent system. HFC-134a is also known as 1,1,1,2-tetrafluoroethane andhas a molecular formula CF₃CH₂F. HFC-134a is VOC exempt; however somestudies have identified it as a contributor to climate change and globalwarming. HFO-1234ze is also known as 1,3,3,3-tetrafluoropropen and has amolecular formula of C₃H₂F₄. HFO-1234ze is a relatively new propellantthat is also VOC exempt, has zero ozone-depletion potential, and has lowglobal warming potential. Unlike traditional CO₂ propellants, both theHFC-134a propellant and the HFO-1234ze propellant typically allow foruniform spray until the aerosol is emptied. Furthermore, both HFC-134aand HFO-1234ze are nonflammable propellants, which traditionally havesprays similar to flammable sprays. A filler material such as boronnitride solids may also be included in the aerosol mixture.

The solvent system and composition of the present invention may beincorporated into a bulk paint system. The bulk paint system preferablyincludes a miscible solvent system, such as the compositions discussedhereinabove, in combination with compatible filler material such asboron nitride powder solids. In one embodiment of the bulk paint system,the system includes a miscible solvent system having between about 10 toabout 90 weight percent PCBTF and between about 10 to about 90 weightpercent fluorinated solvent. In another embodiment of the bulk paintsystem, the system includes a miscible solvent having between about 20to about 40 weight percent PCBTF and between about 60 to about 80 weightpercent fluorinated solvent. In yet another embodiment of the bulk paintsystem, the system includes a miscible solvent having between about 40to about 60 weight percent PCBTF and between about 40 to about 60 weightpercent fluorinated solvent. The bulk paint system of the presentinvention may include between about 1 to about 25 weight percent boronnitride powder and between about 75 to about 99 weight percent misciblesolvent.

The bulk paint system of the present invention may be trans-1,2-DCE freeto reduce or eliminate the presence of VOCs. Alternatively, the bulkpaint system may include trans-1,2-DCE to, as discussed above, utilizeazeotropes and thereby increase the dissolving ability and compatibilityof the bulk paint system with typical binders, suspenders, and viscositymodifiers.

Examples of fluorinated solvents that can be used in the bulk paintsystem of the present invention include HFE 7100, HFC blends such as acombination of 1,1,1,3,3-pentafluorobutane and1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane,1,1,1,2,2,3,4,5,5,5-decafluoropentane with trans-1,2-DCE, and blends ofhydrofluoroethers such as ethyl nonafluorobutyl ether, ethylnonafluoroisobutyl ether, methyl nonafluorobutyl ether, and methylnonafluoroisobutyl ether with or without trans-1,2-DCE. In oneembodiment, the fluorinated solvent includes between about 61 to about63 weight percent 1,1,1,2,2,3,4,5,5,5-decafluoropentane and betweenabout 37 to about 39 weight percent trans-1,2-DCE. In anotherembodiment, the fluorinated solvent includes about 68 to about 72 weightpercent trans-1,2-DCE and about 28 to about 32 weight percent mixture ofhydroflouroethers. Further, in one embodiment, the blend ofhydroflouroethers includes approximately 4 through 16 weight percent ofethyl nonafluorobutyl ether, approximately 4 through 16 weight percentof ethyl nonafluoroisobutyl ether, approximately 2 through 8 weightpercent of methyl nonafluorobutyl ether, and approximately 2 through 8weight percent of methyl nonafluoroisobutyl ether. In one embodimentincorporating hydrofluorocarbons as the fluorinated solvent, the blendof hydrofluorocarbons includes approximately 7 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 93 weight percent1,1,1,3,3-pentafluorobutane. In another embodiment, the blend ofhydrofluorocarbons includes approximately 13 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 87 weight percent1,1,1,3,3-pentafluorobutane.

In an embodiment incorporating a blend of hydroflouroethers, the bulkpaint system includes approximately 84 weight percent miscible solventand approximately 16 weight percent boron nitride powder. In anembodiment incorporating HFE 7100, the bulk paint system includesapproximately 80 weight percent miscible solvent and approximately 20weight percent boron nitride powder. Likewise in yet another embodimentincorporating 1,1,1,2,2,3,4,5,5,5-decafluoropentane, the bulk paintsystem includes approximately 80 weight percent miscible solvent andapproximately 20 weight percent boron nitride powder. In yet anotherembodiment, the fluorinated solvent includes about 90 weight percenttrans-1,2-DCE and 10 weight percent HFE 7100. In another embodimentincorporating an HFC blend, such as a combination of1,1,1,3,3-pentafluorobutane and 1,1,1,2,3,3,3-heptafluoropropane, thesystem includes about 40 through 44 weight percent PCBTF, about 40through 44 weight percent fluorinated solvent, and about 16 weightpercent boron nitride powder.

Additional fluorinated solvents may be used in connection with the bulkpaint system of the present invention either with or without theincorporation of trans-1,2-DCE without departing from the spirit andscope of the present invention. Furthermore, trans-1,2-DCE may beincorporated independent of the fluorinated solvent.

Additives and agents, such as those disclosed above may be incorporatedinto the bulk paint system of the present invention. For example,additives such as benzyl alcohol, butyl carbitol, and/or amyl butyratemay be added to improve paintability and brushability. The bulk paintsystem may incorporate a propellant, such as HFO-1234ze or HFC-134a, forinsertion of the solvent system into an aerosol can for spraying thepaint system. When such additives, agents, and/or propellants areincorporated, the total weight percents of the miscible solvent andboron nitride powder for the entire composition may be proportionallyreduced.

Further, in certain embodiments, it is desirable for the bulk paintsystem to be nonflammable while in alternative embodiments the bulkpaint system may be flammable. Furthermore, in certain embodiments ofthe bulk paint system, the system is VOC free while in alternativeembodiments, the bulk paint system contains VOCs; however, it ispreferred that VOC containing components are incorporated at minimumlevels to reduce the overall levels of VOC in the bulk paint system.

The solvent system and composition of the present invention may also beincorporated into an aerosol system. The aerosol system preferablyincludes a miscible solvent system, such as the compositions discussedhereinabove, in combination with a propellant. The aerosol system may beinserted into an aerosol spray container, such as an aerosol can, forspraying the aerosol system onto a surface. An example aerosol sprayersystem includes a Preval™ system, which may include a butane/propanepropellant. In one embodiment of the aerosol system, the system includesa miscible solvent system having between about 10 to about 90 weightpercent PCBTF and between about 10 to about 90 weight percentfluorinated solvent. In another embodiment of the aerosol system, thesystem includes a miscible solvent having between about 20 to about 40weight percent PCBTF and between about 60 to about 80 weight percentfluorinated solvent. In yet another embodiment of the aerosol system,the system includes a miscible solvent having between about 31 to about33 weight percent PCBTF and between about 67 to about 69 weight percentfluorinated solvent.

The aerosol system of the present invention may include between about 20to about 50 weight percent propellant and between about 45 to about 80weight percent miscible solvent. Further, the aerosol system of thepresent invention may include between about 32 to about 45 weightpercent propellant and between about 46 to about 69 weight percentmiscible solvent.

Examples of propellants that may be used with the aerosol system includeHFO-1234ze and HFC-134a. These propellants are highly beneficial becauseof their nonflammable and low or no VOC properties. Additionalpropellants, including flammable propellants, nonflammable propellants,VOC free propellants, and VOC containing propellants, may be used,however, without departing from the spirit and the scope of the presentinvention. Furthermore, the flammable properties of traditionallyflammable propellant such as butane and propane may be reduced oreliminated when used in connection with the solvent system of presentinvention.

The aerosol system of the present invention may be trans-1,2-DCE free toreduce or eliminate the presence of VOCs. Alternatively, the aerosolsystem may include trans-1,2-DCE to, as discussed above, utilizeazeotropes and thereby increase the dissolving ability and compatibilityof the aerosol system with typical binders, suspenders, and viscositymodifiers.

Examples of fluorinated solvents that can be used in the aerosol systemof the present invention include HFE 7100, HFC blends such as acombination of 1,1,1,3,3-pentafluorobutane and1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane,1,1,1,2,2,3,4,5,5,5-decafluoropentane with trans-1,2-DCE, and blends ofhydrofluoroethers such as ethyl nonafluorobutyl ether, ethylnonafluoroisobutyl ether, methyl nonafluorobutyl ether, and methylnonafluoroisobutyl ether with or without trans-1,2-DCE. In oneembodiment, the fluorinated solvent includes between about 61 to about63 weight percent 1,1,1,2,2,3,4,5,5,5-decafluoropentane and betweenabout 37 to about 39 weight percent trans-1,2-DCE. In anotherembodiment, the fluorinated solvent includes about 68 to about 72 weightpercent trans-1,2-DCE and about 28 to about 32 weight percent mixture ofhydroflouroethers. Further, in one embodiment, the blend ofhydroflouroethers includes approximately 4 through 16 weight percent ofethyl nonafluorobutyl ether, approximately 4 through 16 weight percentof ethyl nonafluoroisobutyl ether, approximately 2 through 8 weightpercent of methyl nonafluorobutyl ether, and approximately 2 through 8weight percent of methyl nonafluoroisobutyl ether. In yet anotherembodiment, the fluorinated solvent includes about 90 weight percenttrans-1,2-DCE and 10 weight percent HFE 7100. In one embodimentincorporating a blend of hydrofluorocarbons as the fluorinated solvent,the blend of hydrofluorocarbons includes approximately 7 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 93 weight percent1,1,1,3,3-pentafluorobutane. In another embodiment, the blend ofhydrofluorocarbons includes approximately 13 weight percent1,1,1,2,3,3,3-heptafluoropropane and approximately 87 weight percent1,1,1,3,3-pentafluorobutane.

Additional fluorinated solvents may be used in connection with theaerosol system of the present invention either with or without theincorporation of trans-1,2-DCE without departing from the spirit andscope of the present invention. Furthermore, trans-1,2-DCE may beincorporated independent of the fluorinated solvent.

Additives and agents, such as those disclosed above and includingsuspenders, binders, and viscosity modifiers, may be incorporated intothe aerosol system of the present invention. Paints and fillers such asboron nitride powder solids and/or metal powders may also beincorporated into the aerosol system creating an aerosol based spraypaint or coating. When such additives, agents, paints, and fillers areincorporated, the total weight percents of the miscible solvent andpropellant for the entire composition may be reduced. In one embodiment,the aerosol system includes about 32 to about 45 weight percentpropellant, between about 46 to about 62 weight percent misciblesolvent, and between about 7 to about 9 weight percent boron nitridepowder.

Further, in certain embodiments, it is desirable for the aerosol systemto be nonflammable while in alternative embodiments the aerosol systemmay be flammable. Furthermore, in certain embodiments of the aerosolsystem, the system is VOC free while in alternative embodiments, theaerosol system contains VOCs; however, it is preferred that VOCcontaining components are incorporated at minimum levels to reduce theoverall levels of VOC in the aerosol system.

The aerosol system of the present invention may have a variety of uses.For example, one composition of the aerosol system may be used as acleaner. Another composition of the aerosol system may be combined withsuspenders, binders, and/or compatible filler material and used as apaint or coating.

Having generally described this instant disclosure, a furtherunderstanding can be obtained by reference to certain specific examplesillustrated below which are provided for purposes of illustration onlyand are not intended to be all inclusive or limiting unless otherwisespecified.

Testing & Examples

The preparation, identification, and testing of example compositions ofthis disclosure are further described below. The particular materialsand amounts thereof recited in these examples, as well as otherconditions and details, should not be construed to unduly limit thisinvention. In these examples, all percentages, proportions and ratiosare by weight unless otherwise indicated.

Testing was initially performed using the above fluorinated solventsalone to determine their ability to act as a carrier or vehicle forpaints and/or coatings. In the tests, the fluorinated solvents werecombined with additives including organic-containing binders,suspenders, and viscosity modifiers that are typically used in paintsand coatings. As discussed above, examples of typical binders and/orsuspenders include cellulosics, including hydroxypropylcellulose orethyl cellulose, and polyvinylpyrrolidone. The viscosity modifiers arepreferably those that are compatible with non-aqueous fluids andliquids, such as organoclays.

HFE 7100 was independently tested but did not dissolve or combine wellwith the organic-containing binders, suspenders, and viscositymodifiers. 1,1,1,2,2,3,4,5,5,5-decafluoropentane was also independentlytested but likewise did not dissolve or combine well with theorganic-containing binders, suspenders, and viscosity modifiers.Fluorinated solvents containing 1,2-DCE were also tested. Specifically,the composition disclosed above and identified under the brand namesVertrel-MCA™ and Novec 72DE™ were each independently tested. Thesecompositions containing a combination of fluorinated solvent withtrans-1,2-DCE had better dissolving abilities likely due to the additionof the trans-1,2-DCE. However, even the fluorinated solvents havingtrans-1,2-DCE in combination with the HFEs and HFCs, did not havesufficient solvency or compatibility with the binders, suspenders, andviscosity modifiers.

PCBTF, which is a VOC-exempt liquid, was also independently testedwithout the addition of HFCs or HFEs. PCBTF dissolved well and wascompatible with typical binders, suspenders, and viscosity modifiersused with paints and coatings.

The combination of PCBTF and fluorinated solvents at varying weightpercents was then tested to determine the dissolving ability andcompatibility with typical binders, suspenders, and viscosity modifiersused with paints and coatings as well as the resulting flash point ofthe composition. The test results of the PCBTF and fluorinated solventcompositions are discussed below.

The flash point of each of the following combinations of PCBTF andfluorinated solvent was tested at Galbraith Laboratories in Knoxville,Tenn. by ASTM D93-11 (Pensky Martens Closed Cup). Combining PCBTF withHFC and HFE fluorinated solvents resulted in a solvent system that wasmiscible in all proportions.

Table I below shows that no flash was observed in a composition having10 weight percent PCBTF and 90 weight percent fluorinated solvent. Thus,these compositions revealed nonflammable solvents.

TABLE I Weight % Flash Component I Weight % Component II Point 10% PCBTF(Oxsol- 90% Combination of about 61-63% No Flash 100 ™)1,1,1,2,2,3,4,5,5,5- Observed decafluoropentane and about 37-39%trans-1,2-DCE (Vertrel-MCA ™) 10% PCBTF (Oxsol- 90% 1,1,1,2,2,3,4,5,5,5-No Flash 100 ™) decafluoropentane (Vertrel-XF ™) Observed 10% PCBTF(Oxsol- 90% HFE 7100 (Novec 7100 ™) No Flash 100 ™) Observed

Table II below likewise shows that no flash was observed in acomposition having 43 weight percent PCBTF and 57 weight percentfluorinated solvent. Thus, these compositions revealed nonflammablesolvents.

TABLE II Weight % Flash Component I Weight % Component II Point 43%PCBTF (Oxsol- 57% Combination of about 61-63% No Flash 100 ™)1,1,1,2,2,3,4,5,5,5- Observed decafluoropentane and about 37-39%trans-1,2-DCE (Vertrel-MCA ™) 43% PCBTF (Oxsol- 57% 1,1,1,2,2,3,4,5,5,5-No Flash 100 ™) decafluoropentane (Vertrel-XF ™) Observed 43% PCBTF(Oxsol- 57% HFE 7100 (Novec 7100 ™) No Flash 100 ™) Observed

Table III below also shows that no flash was observed even in acomposition having 90 weight percent PCBTF and 10 weight percentfluorinated solvent. Thus, these compositions revealed nonflammablesolvents.

TABLE III Weight % Flash Component I Weight % Component II Point 90%PCBTF (Oxsol- 10% Combination of about 61-63% No Flash 100 ™)1,1,1,2,2,3,4,5,5,5- Observed decafluoropentane and about 37-39%trans-1,2-DCE (Vertrel-MCA ™) 90% PCBTF (Oxsol- 10% 1,1,1,2,2,3,4,5,5,5-No Flash 100 ™) decafluoropentane (Vertrel-XF ™) Observed 90% PCBTF(Oxsol- 10% HFE 7100 (Novec 7100 ™) No Flash 100 ™) Observed

The Kauri-Butanol value (“KB Value”) was determined to be 35 for thecomposition having 43 percent PCBTF and 57 percent combination of about61-63% 1,1,1,2,2,3,4,5,5,5-decafluoropentane and about 37-39%trans-1,2-DCE (Vertrel-MCA™). The KB Value is a standardized measure ofsolvent power for a solvent and is governed by an ASTM standardizedtest, ASTM D1133. Typically the higher the Kauri-Butanol value, the moreaggressive or active the solvent is in its ability to dissolve certainmaterials. The KB Value was approximately the proportional compositionaverage KB value for the separate components, which was approximately38. Particularly, the KB Value of PCBTF is 64 and the KB Value ofVertrel-MCA™ is 18. The proportional composition KB Value was derived asfollows:

(43% PCBTF×KB Value PCBTF)+(57% Vertrel-MCA™×KB Value Vertrel-MCA™)

Because the actual KB Value and the proportional composition average KBvalues are nearly the same for the above composition, the approximateactual KB Value of the other PCBTF and fluorinated solvent compositionsset forth herein can likely also be obtained by determining theproportional composition average KB value.

Because the chemistry of a solvent constantly changes as materials aredissolved, it is highly advantageous to have a solvent that remainsnonflammable and miscible across a wide range. The above examples revealthat the combination of a combustible liquid, PCBTF, with HFE and HFCliquids, resulted in a nonflammable miscible solvent over a wide rangeof mixture compositions. Indeed, no change in flammabilitycharacteristics occurred from 10 percent PCBTF to 90 percent PCBTF inconnection with the above fluorinated solvents despite PCBTF alone beinga combustible liquid.

Referring back to the above tables, because PCBTF is VOC exempt and theabove fluorinated solvents not including trans-1,2-DCE(1,1,1,2,2,3,4,5,5,5-decafluoropentane and HFE 7100) are also free ofVOCs, such combinations are highly environmentally friendly and would beclassified as a totally non-VOC liquid. While fluorinated solventsincorporating trans-1,2-DCE would not be VOC exempt because, as statedabove, trans-1,2-DCE contains VOCs, compositions containing lesseramounts of trans-1,2-DCE may be preferred to limit the amounts of VOCs.

While the combinations of PCBTF and fluorinated solvents notincorporating 1,2-DCE performed well and were compatible with typicalorganic binders, suspenders, and viscosity modifiers, they did notperform as well and were not as compatible as the combinationscontaining 1,2-DCE. Thus, potential 1,2-DCE substitutions that were VOCexempt were also tested to determine if high solvency power could beachieved while also maintaining nonflammability and safety forindividuals and the environment.

A composition including approximately 42%1,1,1,2,2,3,4,5,5,5-decafluoropentane, 38% PCBTF, and 20% acetone wastested. The addition of the acetone improved paintability and dryingbehavior and was classified as totally non-VOC. Further, the acetoneimproved the solvent's ability to mix and take in the organic bindersand suspenders. Despite such improved characteristics however, theaddition of 20 percent acetone caused the composition to becomeclassified as flammable with a flash point of less than or equal toabout 39.2 degrees Fahrenheit (4 degrees Celcius). Certain acetoneadditives were incorporated into the composition at a level of 12.5percent of the acetone content in an attempt to reduce the flammabilityof the composition. As shown in Table IV below, flammability insteadincreased with the inclusion of such acetone additives.

TABLE IV Acetone Additive (12.5% Acetone Content) Flash Point Noadditive ≤39.2° F. (4° C.) Octyl Alcohol (CAS 111-87-5) ≤35.6° F. (2°C.) Tea Tree Oil (CAS 68647-73-4) ≤35.6° F. (2° C.) Polyalkylene GlycolDerivative (CAS 9038-95-3) ≤28.4° F. (−2° C.) Alpha Terpineol (CAS98-55-5) ≤28.4° F. (−2° C.)

The solvent systems described herein were further tested to determinewhether a nonflammable aerosol could be prepared. To prepare an aerosolsystem, a propellant additive was combined with the solvent system. Asdiscussed above, 1,1,1,2-tetrafluoroethane, also known as HFC-134a andhaving a molecular formula CF₃CH₂F, may be used as a propellant.Alternatively, 1,3,3,3-tetrafluoropropen, also known as HFO-1234ze andhaving a molecular formula of C₃H₂F₄, may be used as the propellant.Both the HFC-134a propellant and the HFO-1234ze propellant allow foruniform spray until the aerosol is emptied. Furthermore, both HFC-134aand HFO-1234ze are nonflammable propellants but have sprays similar tosprays of flammable propellants. A filler material may also be includedin the aerosol mixture. In one embodiment, boron nitride powder solidswere used as the filler material.

To test the aerosol system for flammability, the aerosol system is addedto an aerosol can. The spray may then be directed into a flame, such asa propane torch, and compared to a similar aerosol can containingstandard flammable propane/butane propellants. Table V below disclosesan example composition of the aerosol system, which was tested forflammability.

TABLE V Appx. Weight % Component 32% HFC-134a propellant 7% Boronnitride solids 22% 1,1,1,2,2,3,4,5,5,5-decafluoropentane 13%Trans-1,2-DCE 26% PCBTF

The amounts set forth in Table V are based upon a solvent compositionhaving 43 weight percent PCBTF and 57 weight percent fluorinatedsolvent. The fluorinated solvent included approximately 62 through 63weight percent 1,1,1,2,2,3,4,5,5,5-decafluoropentane and 37 through 38weight percent trans-1,2-DCE blend (the Vertrel-MCA™ composition).

The aerosol system shown in Table V was compared with a typicalflammable propane/butane propellant. There was no visible flameextension from the aerosol system shown in Table V when directed intothe flame of a propane torch while the propane/butane mixture revealed asignificant torch-like flame. The above aerosol system was also comparedto two commercial aerosol cans purchased from 3M. The first was acontact cleaner having a composition similar to HFE 7100 with theaddition of carbon dioxide. More particularly, the contact cleanerincluded approximately 50 through 70 percent methyl nonafluoroisobutylether, approximately 30 through 50 percent methyl nonafluorobutyl ether,and approximately 1 through 5 percent carbon dioxide. The second was anelectronic degreaser having a composition similar to the composition ofthe brand name product Novec 72DE™ disclosed above and also having asmall amount of carbon dioxide. Specifically, the electronic degreaserincluded approximately 65 through 72 weight percent trans-1,2-DCE,approximately 4 through 14 weight percent ethyl nonafluorobutyl ether,approximately 6 through 16 weight percent ethyl nonafluoroisobutylether, approximately 2 through 7 weight percent methyl nonafluorobutylether, approximately 3 through 8 weight percent methylnonafluoroisobutyl ether, and approximately 1 through 5 weight percentcarbon dioxide. Like the aerosol system set forth in Table V, thecontact cleaner and electronic degreaser had no visible flame extensionwhen sprayed into the flame of a propane torch. The aerosol mixture setforth in Table V was also directed into a candle flame, and observationshowed no visible flame occurred.

Flame extension and flashback testing was also performed on thecomposition shown in Table V by Impact Analytical, Midland, Mich. usingCanadian standards. Particularly, the “Test for Determining theFlashback and the Length of the Flame Projection of a Flammable ProductEnclosed in a Spray Container,” set forth in Consumer Chemicals andContainers Regulations, 2001, SOR/2001-269, Schedule 1. The results ofthe testing revealed that none of the samples produced a flameprojection.

Evaporation and drying rates of solvent systems are frequently relatedto the boiling points for the systems. For example, typically the higherthe boiling point of a solvent system, the longer the evaporation anddrying rates. The boiling point of PCBTF is 282.2 degrees Fahrenheit(139 degrees Celsius) and therefore has a very slow drying rate. Mixingit however with fluorinated solvents, typically having boiling pointsbetween 102.2 degrees Fahrenheit (39 degrees Celsius) and 141.8 degreesFahrenheit (61 degrees Celsius), significantly reduces the evaporationrate or drying time.

FIGS. 1 through 4 disclose schematic diagrams of boiling points ofvarious solvent systems of the present invention. The boiling pointswere measured by Galbraith Labs using ASTMD110-11 standards and as setforth herein. The components of the solvent systems were combined at thedesignated weight percent concentration so that the mixtures weremiscible in all proportions. The mixtures were distilled at ambientpressure (720 to 740 torr) in a concentric tube distillation column andthen allowed to equilibrate at total reflux for at least 60 minutes. Theboiling point of each distillate was measured using a thermocouple.

As discussed above, FIGS. 1 through 4 disclose the different boilingpoints with varying concentrations of PCBTF, denoted as Component B, anda fluorinated solvent, denoted as Component A. At zero percent on thediagram, the composition is entirely Component A, and the boiling pointequals that of the fluorinated solvent. At 100 percent on the diagram,the composition is entirely Component B and would therefore equal theboiling point of PCBTF. The boiling points of 100 percent fluorinatedsolvent and 100 percent PCBTF were not tested and instead were takenfrom readily available Material Safety Data Sheets (MSDS) and relatedliterature on the particular components.

FIG. 1 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent is approximately 62 weightpercent 1,1,1,2,2,3,4,5,5,5-decafluoropentane and approximately 38weight percent trans-1,2-DCE. The brand name of the fluorinated solventtested was Vertrel-MCA™, which has a listed boiling point of 102.2degrees Fahrenheit (39 degrees Celsius). PCBTF has a listed boilingpoint of 282.2 degrees Fahrenheit (139 degrees Celsius). As shown inFIG. 1 and Table VI below (Table VI shows the exact compositions andmeasurements used to generate FIG. 1), the addition of PCBTF to theVertrel-MCA™ fluorinated solvent increased the boiling point of thesolvent system to between 238.6 degrees Fahrenheit (114.8 degreesCelsius) and 274.6 degrees Fahrenheit (134.8 degrees Celsius).

TABLE VI % Component A % Component B (Vertrel-MCA ™) (PCBTF) BoilingPoint 100% 0% 102.2° F. (39° C.) 90% 10% 242.4° F. (116.9° C.) 75% 25%238.6° F. (114.8° C.) 57% 43% 267.4° F. (130.8° C.) 50% 50% 274.6° F.(134.8° C.) 25% 75% 271.0° F. (132.8° C.) 10% 90% 260.4° F. (126.9° C.)0% 100% 282.2° F. (139° C.)

FIG. 2 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent is a blend of hydrofluoroethers(HFEs) including ethyl nonafluorobutyl ether (C₆H₅F₉O), ethylnonafluoroisobutyl ether (C₆H₅F₉O), methyl nonafluorobutyl ether(C₅H₃F₉O), and methyl nonafluoroisobutyl ether (C₅H₃F₉O). Moreparticularly, the blend of HFEs is approximately 68 through 72 weightpercent trans-1,2-DCE, approximately 4 through 16 weight percent ethylnonafluorobutyl ether, approximately 4 through 16 weight percent ethylnonafluoroisobutyl ether, approximately 2 through 8 percent methylnonafluorobutyl ether, and approximately 2 through 8 percent methylnonafluoroisobutyl ether. The brand name of the fluorinated solventblend used was Novec 72DE™, which has a listed boiling point of 109.4degrees Fahrenheit (43 degrees Celsius). As shown in FIG. 2 and TableVII below (Table VII shows the exact compositions and measurements usedto generate FIG. 2), the addition of PCBTF to the Novec 72DE™fluorinated solvent increased the boiling point of the solvent system tobetween 125.4 degrees Fahrenheit (51.9 degrees Celsius) and 232.9degrees Fahrenheit (111.6 degrees Celsius), which was notably less thanthe Vertrel-MCA™ solvent system.

TABLE VII % Component A % Component B (Novec 72DE ™) (PCBTF) BoilingPoint 100% 0% 109.4° F. (43° C.) 90% 10% 125.4° F. (51.9° C.) 75% 25%134.2° F. (56.8° C.) 57% 43% 148.8° F. (64.9° C.) 50% 50% 177.1° F.(80.6° C.) 25% 75% 214.9° F. (101.6° C.) 10% 90% 232.9° F. (111.6° C.)0% 100% 282.2° F. (139° C.)

FIG. 3 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent is methoxy-nonafluorobutane,also known as HFE 7100. The brand name of the fluorinated solvent testedwas Novec HFE 7100™, which has a listed boiling point of 141.8 degreesFahrenheit (61 degrees Celsius). As shown in FIG. 3 and Table VIII below(Table VIII shows the exact compositions and measurements used togenerate FIG. 3), the addition of PCBTF to the Novec HFE 7100™fluorinated solvent only increased the boiling point of the solventsystem to between 146.5 degrees Fahrenheit (63.6 degrees Celsius) and253.2 degrees Fahrenheit (122.9 degrees Celsius).

TABLE VIII % Component A % Component B (Novec HFE 7100 ™) (PCBTF)Boiling Point 100% 0% 141.8° F. (61° C.) 90% 10% 146.5° F. (63.6° C.)75% 25% 157.8° F. (69.9° C.) 57% 43% 169.9° F. (76.6° C.) 50% 50% 171.7°F. (77.6° C.) 42% 58% 177.1° F. (80.6° C.) 25% 75% 200.5° F. (93.6° C.)10% 90% 253.2° F. (122.9° C.) 0% 100% 282.2° F. (139° C.)

FIG. 4 is a schematic diagram of boiling point versus percentconcentration of PCBTF in a solvent system also having a fluorinatedsolvent wherein the fluorinated solvent is1,1,1,2,2,3,4,5,5,5-decafluoropentane. The brand name of the fluorinatedsolvent tested was Vertrel-XF™, which has a listed boiling point of131.0 degrees Fahrenheit (55 degrees Celsius). As shown in FIG. 4 andTable IX below (Table IX shows the exact compositions and measurementsused to generate FIG. 4), the addition of PCBTF to the Vertrel-XF™fluorinated solvent increased the boiling point of the solvent system tobetween 137.5 degrees Fahrenheit (58.6 degrees Celsius) and 244.9degrees Fahrenheit (118.3 degrees Celsius).

TABLE IX % Component A % Component B (Vertrel-XF ™) (PCBTF) BoilingPoint 100% 0% 131.0° F. (55° C.) 90% 10% 137.5° F. (58.6° C.) 75% 25%146.5° F. (63.6° C.) 67% 33% 152.4° F. (66.9° C.) 57% 43% 154.2° F.(67.9° C.) 50% 50% 164.5° F. (73.6° C.) 42% 58% 166.3° F. (74.6° C.) 35%65% 169.9° F. (76.6° C.) 25% 75% 191.5° F. (88.6° C.) 10% 90% 244.9° F.(118.3° C.) 0% 100% 282.2° F. (139° C.)

As shown in the above charts and FIGS. 1 through 4, the PCBTF solventsystem having 1,1,1,2,2,3,4,5,5,5-decafluoropentane combined withtrans-1,2-DCE on average had the highest boiling points while thesystems incorporating the remaining three fluorinated solvents hadsimilar boiling points. The higher boiling point of the PCBTF solventsystem having 1,1,1,2,2,3,4,5,5,5-decafluoropentane combined withtrans-1,2-DCE indicates that this system would have longer evaporationand drying rates, which is often less preferred depending on theintended use of the solvent.

The above compositions set forth in FIGS. 1 through 4 and Tables VIthrough IX were also tested to determine the flash points of therespective solvent systems. Pensky Martens Flashpoint testing complyingwith ASTM D63-11 was performed and no flash was observed for any of thesolvent systems. Thus, the above solvent systems are usable in a numberof applications including for use as a cleaning agent, as part of acleaning composition, or as a paint carrier such as in nonflammableaerosol can formulations.

The evaporation rate of the solvent system having 43 percent PCBTF and57 percent fluorinated solvent having1,1,1,2,2,3,4,5,5,5-decafluoropentane combined with trans-1,2-DCE wasfurther examined for workability in an aerosol can. The system was addedto an aerosol can. Despite having a boiling point of approximately 267degrees Fahrenheit (131 degrees Celsius), the solvent system maintaineda reasonable drying time of approximately five minutes to dry completelyafter spraying onto a surface. This result however indicated that aneven better evaporation rate, such as a rate similar to flammablesolvent based systems incorporating ethyl alcohol and acetone (1-2minutes), may be achievable by incorporating the lower boiling pointfluorinated solvent systems.

Two solvent systems incorporating PCBTF and a blend of HFEs andtrans-1,2-DCE were also tested using aerosol cans to determineevaporation rates. HFO-1234ze was incorporated as the propellant andboron nitride solids were incorporated as the filler material. The exactcomposition by weight percent for each solvent system example are shownbelow in Tables X and XI.

TABLE X Appx. Weight % Example B - Components 32% HFO-1234ze propellant 7% Boron nitride solids 55% HFE blend with trans-1,2-DCE [10% MethylNonaFluoroButyl/NonaFluoroIsoButyl Ether 20% EthylNonaFluoroButyl/NonaFluoroIsoButyl Ether 70% Trans-1,2-DCE]  7% PCBTFLiquid Mix Breakdown (no propellant or solids) 89.2%   HFE blend withtrans-1,2-DCE [10% Methyl NonaFluoroButyl/NonaFluoroIsoButyl Ether 20%Ethyl NonaFluoroButyl/NonaFluoroIsoButyl Ether 70% Trans-1,2-DCE]10.8%   PCBTF

TABLE XI Appx. Weight % Example B - Components 45% HFO-1234ze propellant 9% Boron nitride solids 31% HFE blend with trans-1,2-DCE [10% MethylNonaFluoroButyl/NonaFluoroIsoButyl Ether 20% EthylNonaFluoroButyl/NonaFluoroIsoButyl Ether 70% Trans-1,2-DCE] 15% PCBTFLiquid Mix Breakdown (no propellant or solids) 67.7%   HFE blend withtrans-1,2-DCE [10% Methyl NonaFluoroButyl/NonaFluoroIsoButyl Ether 20%Ethyl NonaFluoroButyl/NonaFluoroIsoButyl Ether 70% Trans-1,2-DCE]32.3%   PCBTF

Example A shown above in table X was very fast drying. ThePCBTF/fluorinated solvent composition (Liquid Mix) of Example Aexhibited a boiling point of approximately 125.6 degrees Fahrenheit (52degrees Celsius). Example B shown above in table XI was slower dryingthan Example B and allowed time for the coating to wet and bond wellwith the surface. The drying time of Example B was approximately 2through 3 minutes, which is approximately the same drying rate as theflammable solvents incorporating ethyl-alcohol or acetone discussedabove. The PCBTF/fluorinated solvent composition (Liquid Mix) of ExampleB exhibited a boiling point of approximately 140 degrees Fahrenheit (60degrees Celsius). Thus a PCBTF/fluorinated solvent composition having aboiling point of approximately 123.8 degrees Fahrenheit (51 degreesCelsius) to approximately 141.8 degrees Fahrenheit (61 degrees Celsius)produces preferred evaporation when using the weight percents ofpropellant and solid levels disclosed in Tables X and XI above andspraying out of an aerosol can. More preferred is a PCBTF/fluorinatedsolvent composition having a boiling point of approximately 125.6degrees Fahrenheit (52 degrees Celsius) to approximately 140 degreesFahrenheit (60 degrees Celsius). And even more preferred is aPCBTF/fluorinated solvent composition having a boiling point ofapproximately 140 degrees Fahrenheit (60 degrees Celsius).

Flame extension and flashback testing was also performed on thecomposition of Example B shown above in table XI by Impact Analytical,Midland, Mich. per US regulations outlined in CFR Part 16, Section1500.45, flame extension and flash back testing per Canadian ConsumerChemicals and Containers Regulations, 2001 (SOR/2001-269), Schedule 1,“Test for Determining the Flashback and the Length of the FlameProjection of a Flammable Product Enclosed in a Spray Container,” andignition distance testing per Regulation (EC) No. 1272/2008 inaccordance with the UN recommendations on the transport of dangerousgoods, manual of tests and criteria, Part III, sub section 31.4“Ignition Distance Test for Spray Aerosols.” The results of the testingusing US, Canadian, and EC test guidelines revealed that none of thesamples produced a flame projection/extension or a flashback ofignition.

The propellant in Composition B shown in Table XI was eliminated todetermine the workability of the composition as a bulk paint, such as abrushable or air-sprayable paint not in an aerosol can. To create a bulkpaint, a paint base such as boron nitride powder, including solids, ispreferably included in the composition. Preferably such solids are addedin amounts up to approximately 25 weight percent of the totalcomposition. Maintaining the same weight percentages minus thepropellants shown in Table XI, a bulk paint was created having acomposition including 16 weight percent boron nitride solids, 27 weightpercent PCBTF, and 57 weight percent HFE blend with trans-1,2-DCE(breakdown shown in table above). The composition was very workable as anonflammable brushable or air-sprayable paint.

The bulk paint of Table XI was also modified by addition of more PCBTFto have a composition including 16 weight percent boron nitride solids,42 weight percent PCBTF, and 42 weight percent HFE blend withtrans-1,2-DCE, which led to better adherence and paintability due to asomewhat slower drying time.

Additional Compositions C, D, and E having no trans-1,2-DCE wereexamined for workability as a bulk paint while maintaining no VOC due tothe elimination of the trans-1,2-DCE. Compositions C, D, and E are shownin Tables XII, XIII, and XIV, respectively below.

TABLE XII Appx. Weight % Example C- Components 20% Boron nitride solids48% 1,1,1,2,2,3,4,5,5,5-decafluoropentane 32% PCBTF Liquid Mix Breakdown(no solids) 60% 1,1,1,2,2,3,4,5,5,5-decafluoropentane 40% PCBTF

TABLE XIII Appx. Weight % Example D - Components 20% Boron nitridesolids 64% 1,1,1,2,2,3,4,5,5,5-decafluoropentane 16% PCBTF Liquid MixBreakdown (no solids) 80% 1,1,1,2,2,3,4,5,5,5-decafluoropentane 20%PCBTF

TABLE XIV Appx. Weight % Example E - Components 20% Boron nitride solids48% HFE 7100 32% PCBTF Liquid Mix Breakdown (no solids) 60% HFE 7100 40%PCBTF

Composition C resulted in a workable bulk boron nitride paint. Becausethe boiling point of the Liquid Mix was approximately 154.4 degreesFahrenheit (68 degrees Celsius), this composition would also likely havea reasonable evaporation rate and therefore work well in an aerosol can.Furthermore, incorporating the HFO-1234ze propellant with Composition Cwould yield a completely non-VOC and nonflammable solvent since bothPCBTF and 1,1,1,2,2,3,4,5,5,5-decafluoropentane are VOC exempt and theLiquid Mix resulted in no flash being observed.

Composition D also resulted in a workable bulk boron nitride paint andincorporating less PCBTF results in a faster drying rate thanComposition C. Like Composition C, Composition D yields a completelynon-VOC and nonflammable solvent since both PCBTF and1,1,1,2,2,3,4,5,5,5-decafluoropentane are VOC exempt and the Liquid Mixresulted in no flash being observed.

Instead of using 1,1,1,2,2,3,4,5,5,5-decafluoropentane as thefluorinated solvent in Composition E, HFE 7100 was incorporated intoComposition E using the same weight percents as Composition C.Composition E resulted in a workable bulk boron nitride paint. Becausethe boiling point of the Liquid Mix of PCBTF and HFE 7100 is slightlyhigher than the Liquid Mix of PCBTF and1,1,1,2,2,3,4,5,5,5-decafluoropentane, Composition E dries slightlyslower than Composition C. Like Composition C, however, Composition Eyields a completely non-VOC and nonflammable solvent since both PCBTFand HFE 7100 are VOC exempt and the Liquid Mix resulted in no flashbeing observed.

A further Composition F shown in Table XI IV below was tested utilizinga blend of HFCs as the fluorinated solvent. Particularly, a combinationof 1,1,1,3,3-pentafluorobutane and 1,1,1,2,3,3,3-heptafluoropropane soldunder the brand name Solkane 365/227™ was used. Composition F resultedin a workable boron nitride paint and test revealed that it was anonflammable composition.

TABLE XIIV Appx. Weight % Example F - Components 16% Boron nitridesolids 42% HFC blend [93% 1,1,1,3,3-pentafluorobutane 7%1,1,1,2,3,3,3-heptafluoropropane] 42% PCBTF Liquid Mix Breakdown (nosolids) 50% HFC blend of 1,1,1,3,3-pentafluorobutane and1,1,1,2,3,3,3-heptafluoropropane (Solkane 365/227 ™) 50% PCBTF

An additional solvent system and bulk paint was tested using a slightlydifferent Solkane 365/227™ blend but the same Liquid Mix/Solidsproportions as shown in Table XIIV. Particularly, an HFC blend ofapproximately 13 weight percent 1,1,1,2,3,3,3-heptafluoropropane and 87weight percent 1,1,1,3,3-pentafluorobutane was used. This compositionalso resulted in a workable boron nitride paint with a nonflammablecomposition and had faster drying times than the HFC composition shownin Table XIIV.

In addition to the components set forth in the above tables andexamples, non-aqueous extender chemicals such as acetone, isopropylalcohol, methanol, and ethanol may be incorporated in varying quantitiesinto the fluorinated solvent systems of the present invention.Furthermore, HFCs and HFEs may contain azeotropes utilizing non-aqueousextenders. Wetting-improvers and compatible additives that give betterflow properties, wetting, and surface coverage onto metal or othersubstrates may also be incorporated without departing from the spiritand scope of the present invention. It is preferred that the addition ofnon-aqueous extender chemicals, wetting improvers, and other compatibleadditives are added in quantities that allow a solvent system tomaintain non-flammability when such system is non-flammable prior tosuch additions. For example, no flash was observed using Pensky-MartensFlashpoint when benzyl alcohol was incorporated at an approximately 1percent level to a solvent system having 43 percent PCBTF and 57 percentfluorinated solvent, wherein the fluorinated solvent included 62 weightpercent 1,1,1,2,2,3,4,5,5,5-decafluoropentane and approximately 38weight percent trans-1,2-DCE. Likewise, no flash was observed usingPensky-Martens Flashpoint when incorporating approximately 1 percentlevels of butyl carbitol, approximately 1 percent levels ofisoamylpropionate, approximately 1 percent levels of isoamylbutyrate,and approximately 1 percent levels of d-limonene independently into thesame solvent system. Despite incorporating only approximately 1 percentof these additives into the solvent system, the flow and wettingproperties of the solvent system onto the surface was significantlyimproved. Moreover, 1 percent levels of benzyl alcohol, butyl carbitol,and amyl butyrate were independently added to Composition F above todetermine if such additions would improve paintability. Benzyl alcoholimproved the brushing ability of the paint on a surface, while butylcarbitol and amyl butyrate did little to aid inpaintability/brushability without the addition of other additives.

While various embodiments and examples of this invention have beendescribed above, these descriptions are given for purposes ofillustration and explanation, and not limitation. Variations, changes,modifications, and departures from the systems and methods disclosedabove may be adopted without departure from the spirit and scope of thisinvention. In fact, after reading the above description, it will beapparent to one skilled in the relevant art(s) how to implement theinvention in alternative embodiments. Thus, the present invention shouldnot be limited by any of the above described exemplary embodiments.

Further, the purpose of the Abstract is to enable the U.S. Patent andTrademark Office and the public generally, and especially thescientists, engineers, and practitioners in the art who are not familiarwith patent or legal terms or phraseology, to determine quickly from acursory inspection the nature and essence of the technical disclosure ofthe application. The Abstract is not intended to be limiting as to thescope of the invention in any way.

What is claimed is:
 1. A bulk paint system comprising: a misciblesolvent including between about 10 to about 90 weight percent PCBTF andbetween about 10 to about 90 weight percent fluorinated solvent; andboron nitride powder.
 2. The bulk paint system of claim 1, wherein saidmiscible solvent includes between about 20 to about 40 weight percentPCBTF and between about 60 to about 80 weight percent fluorinatedsolvent.
 3. The bulk paint system of claim 2 comprising between about 1to about 25 weight percent boron nitride powder and between about 75 toabout 99 weight percent miscible solvent.
 4. The bulk paint system ofclaim 3 further comprising a propellant.
 5. The bulk paint system ofclaim 4 wherein said propellant is HFO-1234ze.
 6. The bulk paint systemof claim 4 wherein said system further comprises an aerosol container,said miscible solvent, boron nitride powder, and propellant within saidcontainer.
 7. The bulk paint system of claim 1, wherein said misciblesolvent includes between about 31 to about 33 weight percent PCBTF andbetween about 67 to about 69 weight percent fluorinated solvent.
 8. Thebulk paint system of claim 1, wherein said miscible solvent includesbetween about 41 to about 50 weight percent PCBTF and between about 50to about 59 weight percent fluorinated solvent.
 9. The bulk paint systemof claim 1 wherein said fluorinated solvent is1,1,1,2,2,3,4,5,5,5-decafluoropentane.
 10. The bulk paint system ofclaim 9 comprising about 20 weight percent boron nitride powder.
 11. Thebulk paint system of claim 1 wherein said fluorinated solvent ismethoxy-nonafluorobutane.
 12. The bulk paint system of claim 11comprising about 20 weight percent boron nitride powder.
 13. The bulkpaint system of claim 1 wherein said fluorinated solvent is acombination including 1,1,1,2,2,3,4,5,5,5-decafluoropentane andtrans-1,2-DCE.
 14. The bulk paint system of claim 13 wherein saidcombination includes between about 61 to about 63 weight percent1,1,1,2,2,3,4,5,5,5-decafluoropentane and between about 37 to about 39weight percent trans-1,2-DCE.
 15. The bulk paint system of claim 1wherein said fluorinated solvent is a combination including a mixture ofhydrofluoroethers and trans-1,2-DCE.
 16. The bulk paint system of claim15 comprising about 16 weight percent boron nitride powder.
 17. The bulkpaint system of claim 15 wherein said mixture of hydroflouroethersincludes ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether,methyl nonafluorobutyl ether, and methyl nonafluoroisobutyl ether. 18.The bulk paint system of claim 15 wherein said combination includesabout 68 to about 72 weight percent trans-1,2-DCE and about 28 to about32 weight percent mixture of hydroflouroethers.
 19. The bulk paintsystem of claim 18 wherein said mixture of hydroflouroethers includesapproximately 4 through 16 weight percent of said combination ethylnonafluorobutyl ether, approximately 4 through 16 weight percent of saidcombination ethyl nonafluoroisobutyl ether, approximately 2 through 8weight percent of said combination methyl nonafluorobutyl ether, andapproximately 2 through 8 weight percent of said combination methylnonafluoroisobutyl ether.
 20. The bulk paint system of claim 1, whereinsaid miscible solvent is trans-1,2-DCE free.
 21. The bulk paint systemof claim 1, wherein said miscible solvent contains trans-1,2-DCE. 22.The bulk paint system of claim 1, wherein said system is nonflammable.23. The bulk paint system of claim 1, wherein said system is VOC free.24. The bulk paint system of claim 1 wherein said fluorinated solvent isa blend of hydrofluorocarbons including 1,1,1,3,3-pentafluorobutane and1,1,1,2,3,3,3-heptafluoropropane.
 25. The bulk paint system of claim 24wherein said miscible solvent includes between about 45 through 55weight percent PCBTF and between about 45 through 55 weight percentfluorinated solvent.
 26. The bulk paint system of claim 25 wherein saidsystem includes about 12 through 20 weight percent boron nitride powderand about 80 through 88 weight percent miscible solvent.
 27. An aerosolsystem comprising the bulk paint system of claim 1 and a propellant,wherein said aerosol system is insertable into an aerosol spraycontainer.
 28. The aerosol system of claim 27 further comprising saidaerosol spray container.
 29. The aerosol system of claim 27 wherein saidpropellant is HFC-134a.
 30. The aerosol system of claim 27 wherein saidpropellant is HFO-1234ze.
 31. The aerosol system of claim 27, whereinsaid system is trans-1,2-DCE free.
 32. The aerosol system of claim 27,wherein said aerosol system contains trans-1,2-DCE.
 33. The aerosolsystem of claim 27, wherein said aerosol system is nonflammable.
 34. Theaerosol system of claim 27, wherein said aerosol system is VOC free. 35.The aerosol system of claim 27, comprising between about 32 to about 45weight percent propellant, between about 46 to about 62 weight percentmiscible solvent, and between about 7 to about 9 weight percent boronnitride powder.
 36. A method of manufacturing a bulk paint systemcomprising the steps of: providing a miscible solvent comprising:between about 10 to about 90 weight percent PCBTF, and between about 10to about 90 weight percent fluorinated solvent; providing boron nitridepowder; and mixing said miscible solvent with said boron nitride powderto create a bulk paint system.
 37. The method of claim 36 furthercomprising the steps of providing a propellant and mixing said bulkpaint system with said propellant to create an aerosol.
 38. The methodof claim 37 further comprising the step of inserting said aerosol intoan aerosol container capable of spraying said aerosol.
 39. The method ofclaim 37 wherein said aerosol mixture is nonflammable.
 40. The method ofclaim 37 wherein said aerosol mixture is VOC free.